DE2223327A1 - Process for the production of condensation products suitable as hardeners for epoxy resins - Google Patents

Description

DIPL.-CHEM. DR. ALFRED SCHÖN

PATEN TA N WÄ Ii T E

II / II

S / I 10-106

Inventa AG for research and patent exploitation, Zurich btampfenbachstr. 38, Zurich, Switzerland

Process for the production of condensation products suitable as hardeners for epoxy resins

The present invention relates to novel condensation products, a process for their production and the use of these condensation products as hardeners for epoxy resins.

Various procedures have been used in the technical and patent literature described for the hardening of epoxy resins, based on the use of condensation products from mono- and / or Dicarboxylic acids and polyamines are based as hardeners. Such processes have been described in, among others, DT-PS 972 757 and 1 105 611, in F-PS 1 157 453, in GB-PS 789 108 and in DT-AS 1 074 856, 1 079 320 and 1 089 544.

According to the information in these references, these have condensation products Aminoamide, imidazoline, or aminoimidazoline structures. Their use as a hardener is supposed to be compared with the use of unmodified polyamines, bring a number of advantages: As a result of lower volatility should the products in processing as less uncomfortable and

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harmful to health. They should also be less be poisonous. Their use aims at the hardening reaction less self-heating occur, and the epoxy resins cured with them should prove to be less brittle .

Despite the stated advantages, however, only the aminoamides obtained from diraerized fatty acids, which are marketed under various names , such as Versamide, Reammide, Casamide, have gained practical importance. All other condensates with polyimines, especially those made from common linear aliphatic ilono and dicarboxylic acids, are hardly ever used.

One of the main reasons for this situation can be found in the fact that in the case of the last-mentioned products the advantages achieved over the simple amine hardeners cannot outweigh the higher price. This higher price is due to the fact that, in addition to the production costs, there are also considerable material costs for the procurement of the required mono- or dicarboxylic acids. It is known that the oxidations of cycloalkanes carried out on an industrial scale with air to cycloalkanols and cycloalkanones produce ilaben products, many of which are complex mixtures of monocarboxylic acids, dicarboxylic acids, oxycarboxylic acids and other, in part, unidentified products. By-products, albeit with a different composition, arise from the oxidation of cycloalkanols and cycloul cannons with?: I lpe tor :; au ro to the corresponding dicarboxylic acids. The techn.l; c: h ·. ■ ' iL Uj;.; Ton processes of this kind are the oxidation \. \ J jlc! IL:.: In never air to cyclohexane ·. ¹ and cyclohexanone and ... WciU :. χ ": yclation of these products with saltpeter.;" arο to . ί [',. _; - :; ϋι ^ ··.;, But also the analogous Oxydati a of C / c] .odoiL: .. i! i Iu ... in! 1OUCiCi. ' Time industrial Kö \ i ■ -λ: Langt.

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BATH ORIGINAL

17th - 21st Weight % 5 - 7th Weight % 3 - 5th Gew. S 6th - 8th Weight % 15th - 18th Weight% 24 - 30 Weight % 14th - 18th Weight %

The amounts of these by-products are very substantial. In the Oxidation of cyclohexane with air to cyclohexanol and cyclohexanone fall, for example, 10 to 20% of the oxidized cyclohexane nls by-products. An approximate analysis of such a lifting product is given below:

Butyric acid 3-5 wt.

Valeric acid

Caproic acid

Succinic acid

Glutaric acid

Adipic acid

Oxycaproic acids

Important identified products

A separation of such components to extract the individual components is usually uneconomical. As far also Keina other use of such products was found next to n'isl their removal is difficult, they need to be uneconomic ?. Way to be incinerated as waste, which leads to additional pollution.

It has now been found, surprisingly, that condensation products which are extremely inexpensive as waste products and also ideally suited as hardeners for epoxy resins are, can be prepared if the resulting in the oxidation of cycloalkanes, with primary and secondary amines Reactable lifting products condensed with polyvalent aliphatic amines.

'.'. The qla e success of this process is insofar as rapid -.->: \ r <.; o byproducts ^ii:. There are also complicated mixtures of components that have not even been identified, but also with percentages c, nf rllcn, v / eiche in relation to _t "the present statement for the purpose of foreign profit of cycloalkanols, cycloalhanones and dicarboxylic acids we opti.mievL · v; ovden are.

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BAD ORKäiNAt

The latter can be shown in a very striking way: butyric acid, adipic acid and that described in more detail below As "waste acid mixture B" designated by-product were by the same method with 2 moles of the aliphatic Amine: triethylenetetramine condensed together per mole of carboxyl group, with the unreacted subsequently Amine was distilled off. The three condensation products thus obtained and, as a further comparison substance, the triethylenetetramine itself, were treated with an epoxy casting resin based on 2,2-bis (p-hydroxyphenyl) propane ("bisphenol-A") and epichlorohydrin with an epoxide equivalent weight of 195 mixed in the proportions that always as exactly one Epoxy group was present per amine hydrogen atom. This relationship In the case of the condensate from the waste acid mixture B, it was not possible to calculate exactly, which is why a series of mixtures with this product (see table below). After hardening of the batches for 12 hours at 20 ° C and then 4 hours at 120 ° C., the following impact strengths according to DIN 53 45 3 were found.

Condensation product
(Harder) g condensation pro
product per 100g epoxy
resin (bisphenol A) Impact strength TETA 13.4 2
8.7 cm kg / cm Condensate from butter
acid + TETA 29.6 2
15 cm kp / cm Condensate from adipine
acid + TETA 26.4 2
8 cm kp / cm

Condensate from waste acid B + TETA

36.5
40
45
55

23 24 39 21

TETA = triethylenetetramine

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In all cases, the condensate from the waste acid proved to be the same as the condensates in terms of impact strength Components than superior. This synergism is surprising.

One of the advantages of the condensation products according to the invention is based on their low vapor pressures. Prove thereby During processing, the products prove to be less harmful, dangerous and annoying than those used in their manufacture used aliphatic polyvalent amines. In addition, they are sensitive to carbon dioxide and moisture significantly lower than that of the aliphatic polyamines. Some of the products that can be made according to the invention have viscosities of only a few poise at room temperature, which makes them particularly easy to combine with liquid epoxy resins let process »

Hardeners with similarly good properties were already known, but could never be anywhere near as economical getting produced"

The condensation products produced according to the invention can therefore be regarded as highly refined polyamine hardeners ρ which generally about 50% and more of the previously worthless by-products of cycloalkane oxidation in chemically bonded form Shape included. Since, as can be seen from the subsequent process description, their production is carried out with little effort can be, the products obtained according to the invention are cheaper than those already inexpensive in themselves Output amine.

Accordingly, the condensates according to the invention are especially important for those applications in which economic and economic aspects are in the foreground. Road surfaces, floor coatings or the like. Are examples of such applications.

ύ / 'i J / o

As Amir; a for the production of the condensation products according to the invention "In principle, all polyvalent aliphatic amines can be used, such as the compound

However, the best results are obtained when used of amines of formula I.

- (Nil — A ^ -NH, {I}

In it mean

A is a lower alkylene radical which has 2 carbon atoms and is bonded to the neighboring members with different carbon atoms, and r; Z to 6, especially 2-4. A appearing η-fold can be the same or different »They are therefore amines, which in practice are referred to as" polyalkylenepolyamines ".

Preferred such amines εϊίιά, diethylenetriamine, triethylenetetramine and bis- (S-aminopropyLi ~ imine.

As by-products by definition from the oxidation of cycloalkanones for the. Preparation of the condensation product according to the invention First and foremost, the by-products are used larger; Amounts in the oxidation of cyclohexane, methylcyclohexane or CyclcdodGcar »Kit with atmospheric oxygen. These are beneficial burned off the main products of this oxidation by extraction with aqueous alkali solutions, and then isolated by acidification and extraction of the vesorous solutions, so that the main thing is to use acidic products, above all Has mono- and dicarboxylic acids, it should be noted that not only the composition of the isolated by-product and thus also the properties of the condensate produced from it

i υ S ~ 2 fe ü ■■; »· 'Ο

* 7

of the type of the oxidized cyeloalkane, the oxidizing agent and from the management of the oxidation process, but also from that of the extraction of the by-products from the acidified Alkali solution depends on the solvent used.

For example, when cyclohexane is oxidized with air, by-products according to the table above are obtained when the aqueous-alkaline Extract is extracted after acidification with methyl ethyl ketone. However, irsl this extraction is cyclohexane is used, a product is isolated which contains more monocarboxylic acids and fewer dicarboxylic acids than when using Methyl ethyl ketone.

Other by-products which can be reacted with said amines to form condensates which can be used according to the invention are obtained in the oxidation of cycloalkanones and cycloalkanols (which are obtained by oxidation of cycloalkanes with oxygen) with nitric acid. After the dicarboxylic acids produced in this way have crystallized out, they are in solution in the mother liquor and can be obtained from this by evaporation " further crystallization or extraction" DSώ - ³ ^ obtained by-products contain, inter alia, particularly large amounts of dicarboxylic acids.

As can be seen from the foregoing, the by-products to be used according to the invention are obtained in a broad spectrum of compositions. This makes it possible to produce a large number of condensates with the most varied of properties on this basis and by choosing the appropriate amine, so that a particularly suitable condensate can be found for every application. If necessary, by-products of different origins can also be blended with one another before the condensation in order to achieve special combinations of properties, or different condensates can be mixed with one another.

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Particularly suitable hardeners can be obtained if you use the preferred ones Reacts amines with the preferred by-products.

Basically you have the possibility to get help with: Methods / like distillation, crystallization or extraction, dl-! Composition of the mentioned by-products into a desired one Move towards right. On the other hand, modifications can also be made of the condensates obtained achieved by the fact that the by-products used according to the present invention additives, such as e.g. fatty acids, added v / ground.

For the production of the condensation products according to the invention the starting components are used in such a ratio that that per equivalent acidimcrically titratable acid group des waste product used at least two amino groups of the polyamine There are, however, mostly 2 to 8 flol of the polyamine used per acid equivalent, since this gives lower viscous condensates with better processability. Even larger amounts of amine generally do not lead to any significant amounts Changes in the properties of the condensates are more detrimental to the economic efficiency of the process.

To carry out the condensation, the outputs are preferably components together under a protective gas, preferably nitrogen, heated to temperatures between 150.degree. C. and 330.degree. C. for 1 to 6 hours. What is formed in the reaction distills Water off.

Based on the state of the art, today's standards must be assumed, that in these condensations the present carboxyl ur.c Amino groups react to form amides, and that also, especially when using higher condensate capacities, imidazoline structures develop. Since, however, the no. Portion used mixtures still a large number of other: fractional groups, such as Hydror.yl- and Ccrbcnyigruppen, cntha.vt ^ n, is to be assumed that during the Kondonsatxon still further P.cr'rL.i onca run, over their Nature today can only be guessed at.

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BADORiGiNAL

The condensation pio-.1v.:. can be used directly as IrIrLf;.: i'ür Epo.::Ldhar~o Uu / -den. Out is men cbcr vorsAcx : · .λ, unconverted Arain vx \ z your Kculen ^ aticnsprodukt, if necessary under vacuum, to distill off. This is especially true if there is a relatively large amount of free izxins rc "h according to the ranking. Da. idlich again in cliicia next approach vcrv / cndet v / srdo.i; whereby the Pro2Oi3 can also be designed continuously.

Epoxy resins, which are to be used according to the invention with Condensation products that can be hardened are compounds with less than one epoxy group per molecule. Your manufacture takes place preferably through the action of epihalohydrins or dihalohydrins to polyhydric alcohols or mononuclear or polynuclear phenols, especially those of the type of 2,2-bis (p-hydro: cyphenyl) propane ("bisphenol A") in the presence of alkali. You can continue through such connections obtained direct epoxidation of suitable compounds with more than one double bond per molecule.

Since the composition and structure of the invention Condensation products is not exactly known, must be used for the production of curable wet with the desired Properties to be used mixing ratio of epoxy resin and condensation product according to the definition determined empirically v / earth. Said hardenable compositions are prepared in a generally known manner by simple mixing of the epoxy resin at room temperature, possibly also at a slightly elevated temperature, with one of the inventive Condensation products. These mixtures can also contain other components, such as fillers, pigments, dyes, Accelerators, plasticizers or reactive thinners or the like.

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BATHROOM 0RK3JNAL

For the production of solvent-containing two-component components: n- strokes are particularly suitable for scrj. "in situ" adducts of eggs Kondencata. Π> lc'ic adducts have been known to be ir. Manufactured the way that the hardener is made with epoxy compounds in an amount that is not sufficient for the formation of crosslinked products, preferably in the presence of solvents, is reacted. Shortly before the relationship, then ground these "in situ" adducts with the Epo :: l ·.! harunenge, shows in the form of a solution, blurred.

The hardening of the epoxy resin / detergent mixture takes place even at a room temperature, with the development of heat. It can be accelerated by heating. In some of the Syjj.c: -: o has a lJachtenpo: _- n fortigen the products at 70 ° C to 150 ⁰ C for the full development of erv / ünschten Eigonscha '- th as proven advantageous. In other cases, especially \: ~ λ:.. A Nachtempörn not r 'is üglich, also the Zucat proves ^ one of the known accelerators useful.

The following examples illustrate the invention.

In all examples, the epoxy resin used is one based on 2,2-bis (p-hydroxyphenyl) propane and epichlorohydrin.

Obtaining the starting acids (those with the definition

Amines converted into the hardeners to be used according to the invention the)

I Cyclohexane is oxidized as co-naphthenate with air at 160 ^° C. and 10 atm pressure in the presence of 1 ppm of Co, so that a conversion of 6.5% (based on cyclohexane) results. The reaction product is washed with a 10% aqueous sodium hydroxide solution and the aqueous phase is acidified with sulfuric acid. Half of the acidified mixture then becomes

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?) _ r.it Cyelohcxan extracted. With the removal of the Cyclohor'c: \ - we get a "acid number" of 422 (ng KOil / g egg) and an acid equivalent weight of 133 g.

b) _ The other half ca is extracted m.i ": IIoLhyla ^ ylkoton. After de :; Removal of the Ilethyläthylkotons becomes an "acid mixture B" with an euro number of <i35 (ng KOII / g Siluremixture) and one

chi: received from 12Ug.

If this acid mixture is distilled from B to 50 ° C. and 3 Torr, so one obtains the acid mixture A.

II) Cycloxane is with air at 185 ° C and a pressure of 15 atm in;. 'r .- / escihcsit of KatalycJcLoren oxidized until a conversion of 4 & is reached. The Reck'-ionGprodu ^ it is made with an aqueous Washed dry sodium hydroxide solution and the aqueous phase with sulfur acidified. From the acidified solution becomes

rO_ one half extracted with ethyl ethyl ketone. After Removal of the solution part becomes an "acid mixture C" with an acid number of 362 (iag KOII / g acid mixture} and one Obtained acid equivalent weight of 155 g.

b) _ The other half is first with cyclohexane and then extracted with I Is thy läthy! ketone. From the diethyl ketone extract the solvent is removed. Ilan receives an "acid mixture D" with a SHurc number of 3OO (mg KOH / g acid mixture) and one Acid equivalent / not of I-J7g.

III) CycJciiodeccn is made with Lulu LjI slightly increased pressure and IGO ⁰ C in G ^ gciv-. 'Kind of Borvci: b.Li-dungcn _r as boric acid, oxiüic.; T. With a previously prepared ash for separating the boric acid, the acidic portions of the reaction mixture were washed with an aqueous alkali solution. Since in this alka-

209849/1176 BAO

ical wash water also Hcutraltcile (for example ester) are emulsified, it is boiled for 2 h to remove the Saponify esters. The alkaline wash water is then diluted with water and cooled to room temperature. the The main amount of the IJcutraltcile precipitates and can be filtered off v / earth. In order to get the remaining hydrocarbons out of the alkali wash, the oil is then stepped with methyl ethyl ketone extracted several times. The aqueous alkaline phase is then acidified with sulfuric acid and the released carboxylic acids v / earth extracted with methyl ethyl ketone. From the extract the solvent is removed. Ilan receives an "acid mixture E" with an acid number of 255 (mg I'OH / g acid mixture) and an acid equivalent weight of 220 g.

example 1

A) Manufacture of the condensation product (hardener)

11 GB g of triethylenetctranine (8 Hol) are poured into a 3 l flask. The flask is fitted with a thermometer, a distillation bridge and a !! "pipe. 266 g of "Acid Mixture A" (2 equivalents) are added. True.-J. The internal temperature rises to 100 ° C after the addition of the silure mixture. The reaction mixture is then heated up to 200 ° C. under nitrogen within 4 h. The condensation water begins to distill off at a product temperature of 160 - 170 °. 59 g of condensation water and neutral parts are transferred. 925 g of excess amine are then distilled off at 0.2 now vacuum and up to 150 ^° C. bottom temperature. 450 g of oily light yellow product remain as a residue with an amine number of 634 mg / KOH / 1 g of Prou \: k; -. and a viscosity at 25 ° C of 520 cP.

B) curing of epoxy resin

The following mixtures of a liquid epoxy resin (epoxidized: 0.52 A'q./100 g resin; Viscosity at 25 ° C: 11000 cP) and the im

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The hardeners described in the previous section are produced in the weight ratios given in the table below and cured for 12 hours at 20 ° C and 4 hours at 120 ° C. The impact strengths and the heat resistance according to Martens of the cured test specimens (120 mm 10 mm χ 15 mm) are:

g hardener
100g epoxy resin Impact strength
(DIN 53 453)
(Kp.cm/cm ² ) Marten temperature
(DIN 53 458) ( ⁰ C) 30th
33.8
40
45 13th
27
17th
23 76
71
68
63

To use the condensation product prepared according to this example (Hardener) when used for 2-component epoxy resin lacquers, the following mixtures are produced:

a _) _ To prepare an "in-situ" adduct solution, 45.0 Parts by weight of the hardener prepared according to this example, 24.0 parts by weight of xylene and 6 parts by weight of n-butanol below Stirring with 25.0 parts by weight of a solid epoxy resin (epoxy value: 0.195-0.22, softening point: 64-74 ° C, epoxy equivalent: 500) offset. The reaction mixture is then stirred at 80 ° C. for 1 hour.

In this way, a 70% "in situ" adduct solution is used a Η equivalent of 165 and a viscosity of 956 cP at 2 5 ° C obtained.

To 100 parts by weight of a solvent-based epoxy resin varnish , which contains 50 percent by weight of the previously described epoxy resin (epoxy equivalent: 500 etc) are used for the purpose

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Hardening 16.5 parts by weight of the above adduct solution added. The solvent consists of 25 parts by weight of a technical xylene mixture, 10 parts by weight of methyl isobutyl ketone, 5 parts by weight of ethylene glycol monomethyl ether, 5 parts by weight of methyl isobutyl carbinol and 5 parts by weight a 55% melamine resin solution in n-butanol. After Application and curing are obtained with glossy and flawless film surfaces.

b) 100 parts by weight of a liquid epoxy resin (epoxy value: 0.52 equivalents per 100 g of resin; viscosity at 25 ° C.: 11000 cP) are mixed with 34 parts by weight of the hardener described above and 20 parts by weight of benzyl alcohol. The solvent-free lacquer obtained results in tack-free and fault-free film surfaces after curing.

Properties of the films obtained

1) Hardening process:

We determine ^ the increase in surface hardness according to DIN 53157; König pendulum hardness at 20 ° C; Test specimens are coated glass plates.

Epoxy resin hardener system Curing time in days
1 2 3 7 14 21 a) solvent-based '
System with adduct hardener 61 120 120 137 172 172 2)
b) solvent-free '
system 81 120 148

1) Dry film thickness 100

2) Dry film thickness 300 μm

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2) Erichsen depression

The elasticity, the extensibility and the adhesiveness of the films are examined according to the Erichsen method (DIN 53 156) Test specimens are coated iron sheets 110 χ 70 χ 1 mm.

Epoxy resin hardener system Curing time in days
7 14 21 a) solvent-based
System with adduct hardener 10.1 10.1 2)
b) solvent-free
system 7.6 7.5

1) dry film thickness 80-90 jam

2) 300 yum dry film thickness

3) ketone test

In order to assess the behavior of the films against organic solvents, the "ketone test" is carried out, which is the hardened one Film immersed in methyl isobutyl ketone for 20 minutes. The softening is checked by means of a pendulum hardness test.

Epoxy resin hardener system Pendulum hardness according to König
(DIN 53 157) ₂₎
Before ketone test ^J 'after ketone test' a) solvent-based '
System with adduct hardener 172 171 2)
b) solvent-free
system 148 147 '

1) Dry film thickness: 100

2) Dry film thickness: 300 μτα.

3) after 21 days Häx ± unrrsz £ it- ~

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Example 2

399 g of acid mixture A (3 equivalents) and 618 g of diethylenetetramine (6 mol) are condensed together in the same way as in Example 1, 109.5 g of water of condensation, neutral parts and Skip Amin. The remaining excess amine is then distilled off at 0.2 mm vacuum and up to 140 ° C. bottom temperature. The amount of amine distilled off is 405.5 g. The yield is 502 g of oily light brown product that remains as a residue, with an amine number of 359 mg KOH / g product and a viscosity at 25 ° C. of 1060 cP.

The following mixtures of a liquid bisphenol A epoxy resin (epoxy value: 0.52 eq. / 100 g resin; viscosity at 25 ° C: HOOOcP) and the product described in this example are made and cured for 12 hours at 20 ° C and 4 hours at 120 ° C. The impact strength and the heat resistance according to Martens of the cured test specimens (120 mm 10 mm χ 15 mm) are:

g condensation
product
100 g epoxy resin Impact strength
(DIN 53 453)
(Kp.cm/cm ² ) Martenstemp.
(DIN 53 458)
( ⁰ C) 37.7
45 16
19th 72
60

Example 3

532.0 g of acid mixture A (4 equivalents) and 2336.0 g of triethylenetetramine (16 mol) are condensed together at 250-270 ° C. The condensation and the subsequent distillation of the excess amine are carried out in the same way as in Example 1 carried out. 22 4 g of condensation water, neutral parts and amine distill over during the condensation. The total amount of the

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recovered amine is 1580 g. The yield is 663.5 g of oily light yellow product, which remains as a residue, with an amine number of 634 mg KOH / 1 g product and a viscosity at 25 ° C. of 173 cP.

The following mixtures of a liquid bisphenol A epoxy resin (epoxy value: 0.52 eq. / 100 g resin; viscosity at 25 ° C: 11000 cP) and the product described in this example are made and cured for 12 hours at 20 ° C and 4 hours at 120 ° C. the Impact strengths and the heat resistance according to Martens of the cured test specimens (120 mm 10 mm χ 15 mm) are:

g condensation
product
100 g epoxy resin Impact strength
(DIN 53 453)
(Kp.cm/cm^) Marten temperature
(DIN 53 458)
( ⁰ C) 37
40 20th
21 76
74

Example 4

322 g of acid mixture B (2.5 equivalents) and 730 g of triethylenetetramine (5 mol) are condensed together. The condensation and the subsequent distillation of the excess amine are carried out in exactly the same way as in Example 1. 85 g of condensation water and neutral parts are transferred during condensation. The amount of amine distilled off is 417 g. The yield is 550 g of brown, highly viscous product, which remains as a residue, with an amine number of 331 mg KOH / g product and a viscosity at 25 ° C of 260 P.

The following mixtures of a liquid bisphenol A epoxy resin (epoxy value: 0.52 eq. / 100 g resin; viscosity at 25 ° C: 11000 cP)

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and the product described in this example are prepared and 12 h at 20 ⁰ C and cured 4 hours at 120 ° C. The impact strengths and the heat resistance according to Martens of the cured test specimens (120 mm 10 mm χ 15 mm) are:

g condensation
product
100 g epoxy resin Impact strength
(DIN 53 453)
(Kp.cm/cm^) Marten temperature
(DIN 53 458)
( ⁰ C) 36.5
40
45
55 23
24
39
21 87
71
75
62

Example 5

620 g of acid mixture C (4 equivalents) and 1168.0 g of triethylenetetramine (8 moles) are condensed together. The condensation and subsequent distillation of the excess amine are carried out in exactly the same way as in Example 1. 185.0 g of condensation water and neutral parts go to the Condensation over. The amount of amine distilled off is 719.0 g. The yield is 884.0 g of brown viscous Product, which remains as a residue, with an amine number of 39 3 mg KOH / g product and a viscosity at 2 5 ° C of 72 P.

The following mixtures of a liquid bisphenol A epoxy resin (epoxy value: 0.52 eq / lOO g resin; viscosity at 25 ° C. 11000 cP) and the product described in this example are prepared and 12 h at 20 ⁰ C and 4 h hardened at 120 ^° C., the impact strengths and the heat resistance according to Martens of the hardened test specimens (120 mm 10 mm χ 15 mm) are:

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g condensation
product
100 g epoxy resin Impact strength
(DIN 53 453)
(Kp.cm/cm ² ) Marten temperature
(DIN 53 458)
(° C) 35
40
45
50 17th
17th
21
17th ■ 87
82
80
73

Example 6

880 g of acid mixture D (4.7 equivalents) and 1375 g of triethylenetetramine (9.4 moles) are condensed together. The condensation and subsequent distillation of the excess Amines are carried out in exactly the same way as in Example 1. 310 g of condensation water and neutral parts are included condensation over. The amount of amine distilled off is 755 g. The yield is 1090.0 g of a brown one viscous product, which remains as a residue, with an amine number of 393 mg KOH / g product and a viscosity at 25 ° C from 625 P.

The following mixtures of a liquid bisphenol A epoxy resin (epoxide value:. O, 52 eq / lOO g resin: viscosity at 25 ° C: HOOOcP) and the product described in this example are prepared and 12 h at 20 ⁰ C and 4 h at Cured at 120 ^{° C.} The impact strengths and the heat resistance according to Martens of the cured test specimens (120 mm 10 mm χ 15 mm) are:

g condensation
product
100 g epoxy resin Impact strength
(DIN 53 453)
(Kp.cm/cm ² ) Marten temperature
(DIN 53 458)
( ⁰ C) 35
41.1
45 19th
19th
17th
! RAG / 1 176 95
89
86

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Example 7

484.0 g of acid mixture E (2.2 equivalents) and 257.0 g of triethylenetetramine (17.6 mol} are condensed together at 250 ° C - 270 ° C The condensation and the subsequent distillation of the excess amine are carried out in the same way as in Example 1. 110 g of condensation water and neutral parts and amine are transferred during the condensation. The amount of distilled Amine is 2374 g. The yield is 570 g of brown viscous product, which remains as a residue, with an amine number of 387 mg KOH / g product and a viscosity at 25 ° C from 110 p.

The following mixtures are used to use this condensation product when used for 2-component epoxy resin paints manufactured:

a) 100 parts by weight of a liquid bisphenol A epoxy resin (Epoxy value: 0.52 equivalents / 100 g resin) are mixed with 60 parts by weight of this condensation product. Of the The solvent-free varnish obtained has a pot life of 4 hours and 30 minutes and, after curing, results in tack-free Films and flawless surfaces.

b) 100 parts by weight of an epoxy resin solution containing 50% by weight of epoxy resin (epoxy value: 0.22 equivalents / 100 g of resin), with 12 parts by weight of this condensation product mixed. The solvent-based paint obtained has a pot life of > 2 days and after hardening results in non-sticky and flawless surfaces.

c) To produce an "in situ" adduct solution, 45.4 parts by weight of the product produced according to this example, 32.0 parts by weight of xylene and 8 parts by weight of n-butanol are mixed with 14.6 parts by weight of a solid epoxy resin with an epoxy equivalent of 500 while stirring offset. The reaction mixture is then 1 h at 80 ⁰ C after-

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touched. In this way, a 60% "in situ" adduct solution with an H equivalent weight of 280 and one Obtained viscosity of 2950 cP at 25 ° C.

100 parts by weight of a solvent-based epoxy resin paint, The 50 wt.% Epoxy resin (epoxy equivalent = 500) contains, 28 parts by weight of the above are used for curing Adduct solution added. The adduct solution obtained has a pot life of 2 days and, after curing, results in tack-free shiny and flawless film surfaces.

The films obtained have the following properties: 1) Course of hardening

The increase in surface hardness is determined

DIN 53 157;

Pendulum hardness according to König at 20 ⁰ C:

Epoxy resin hardener systems solvent-free
system 1 2 Time
7th in days
18 30 266 a) solvent-based
system 32 152 186 230 212 3) solvent-based
System with adduct hardener 32 90 147 180 210 c) 58 116 172 198

Test specimens are coated glass plates.

The dry film thicknesses are for

System a) solvent-free system b) solvent-based system c) adduct varnish

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250-300 pm 35-40 ^ around 50-60 μια

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2) Erichsen depression

The elasticity, the ductility and the Adhesion of the films according to the Erichsen method (DIN 53 156)

Epoxy resin hardener systems Curing time in days at 20 ° C
and artificial aging
7 days 7 days 20 ° C 7 days 20 ° C
20 ⁰ C +11 days +11 days
at 60 ° C at 100 ⁰ C a) solvent-free
System 1) 1.4 0.9 1.4 a) solvent-containing
System 2) 9.8 8.5 8.9 c) solvent-containing
System with adduct
harder 3) 10.4 9.4 9.5

D. Dry film thickness 250-300 ;around 2) Dry film thickness 35-40 ^ in 3) Dry film thickness 60-70 around

Test specimens are coated iron sheets 110 χ 70 χ 1 mm.

3) ketone test

The "ketone test" is used to assess the behavior of the films against organic solvents. The hardened Film immersed in methyl isobutyl ketone for 20 minutes. The softening is checked by means of a pendulum hardness test.

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Epoxy resin hardener systems solvent-free s'
system Pendulum hardness according to
before ketone test 4) king
after (DIN 53 157)
Ketone test a) solvent-based ²⁾
system 226 215 b) solvent-containing '
System with adduct hardener 212 205 c) 198 167

1) Dry film thickness ^ j 250 pm

2) Dry film thickness / ~ v / 40 / im

3) Dry film thickness r * j 60 / im

4) after 30 days of curing time

Example 8

451.5 g of acid mixture B (3.5 equivalents) and 1442.0 g of diethylenetriamine (14.0 mol) are condensed together in the same way as in Example 1, 108.0 g of water of condensation, neutral parts and amin pass over. The excess amine is then used distilled off at 0.2 mm vacuum and up to 140 ° C. bottom temperature. The amount of amine distilled off is 1268.5 g. The yield is 517.0 g of brown, viscous product, which is the residue remains, with an amine number of 328 mg KOH / g product and a viscosity at 25 ° C of 1657 P.

To prepare an "in situ" adduct solution, 44 parts by weight of the product prepared according to this example, 32 parts by weight n-butanol and 8 parts by weight of xylene with stirring with 16 parts by weight of a solid epoxy resin with one epoxy equivalent offset by 500. The reaction mixture is then

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send stirring at 80 ° C. for 1 h. In this way, a 60% "in situ" adduct solution with a Η equivalent of 260 and a viscosity of 3100 cP at 25 ° C.

100 parts by weight of a solvent-based epoxy resin paint, which contains 50% by weight of epoxy resin (epoxy equivalent = 500), 26 parts by weight of the above adduct solution are used for curing added. After application and curing, coatings with glossy and flawless film surfaces were obtained, have the following properties:

1) Course of hardening

The increase in surface hardness is determined in accordance with DIN 53 157; König pendulum hardness at 20 ° C:

Hardening time in days 1 2 3 7 14 Pendulum hardness according to König 42 1ÖÖ lÖÖ 147 177

Test specimens are coated glass plates. The dry film thickness are 80 - 90 yum.

2) Erichsen depression

The elasticity, the extensibility and the adhesion of the films are examined according to the Erichsen method (DIN 53 156). Test specimens are coated iron sheets 110 χ 70 χ 1 mm. The dry film thicknesses are 50-60 ^ Lim.

Hardening time in days 7 14

Erichsen depression 10.8 10.5

Example 9

1995 g of acid mixture A (15 equivalents) and 2190 g of triethylenetetramine (15 moles) are condensed together. The condensation is carried out in exactly the same way as in Example 1.

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51Og condensate water and neutral parts go with the condensation above. The yield is 3675 g of brown oily product, which remains as a residue, with an amine number of 654 mg KOH / g product and a viscosity at 25 ° C of 680 cP.

40 g of this product are mixed with 100 g of a liquid bisphenol Α epoxy resin (epoxide value: 0.52 Xq./100 g resin; viscosity at 25 ° C: 11,000 cP) and mixed for 12 h at 20 ° C and 4 h at 120 ⁰ C hardened. The impact strength (DIN 53 453) of the cured test specimens (120 mm 10 mm 15 mm) is 15 Kp.cm/cm ² , the heat resistance according to Martens (DIN 53 458) 65 ° C.

Example 10

To 100 parts by weight of the hardener prepared according to Example 9, 55.5 parts by weight of a liquid epoxy resin are added with stirring based on bisphenol A (epoxy equivalent: 190) (GRILONIT G 3, Emser-Werke AG, Switzerland) slowly given. The reaction mixture is then stirred at 100 ° C for 1 hour. The viscous adduct hardener obtained in this way is light yellow. Its H equivalent is 106.

Use of this adduct hardener for 2-component epoxy resin paints as well as 2-component epoxy resin tar paints

100 parts by weight of the liquid epoxy resin mentioned in Example 10 based on bisphenol A (epoxy equivalent: 190, viscosity at 25 ° C: 11000 cP) with 56 parts by weight of the adduct hardener described in Example 10 and 29 parts by weight of benzyl alcohol mixed. The solvent-free After curing, lacquer results in tack-free, clear and fault-free film surfaces.

100 parts by weight of EPIKOTE 162 (Shell Chem. Corp., USA), an aliphatic Epoxy resin based on pentaerythritol polyglycidyl ether

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with an epoxy number of 0.62 epoxy equivalent per 100 g of resin, 66 parts by weight of that described in Example 10 are used Adduct hardener and 34 parts by weight of benzyl alcohol mixed. The solvent-free varnish obtained results after curing tack-free, clear and flawless film surfaces.

50 parts by weight of the liquid epoxy resin mentioned in Example 10 based on bisphenol A (epoxy equivalent: 190, viscosity at 25 ° C.: 11000 cP) and 50 parts by weight of glycerol polycidyl ether (Epoxy number: 0.86-0.72, epoxy equivalent per 100 g of resin) are 66 parts by weight of that described in Example 10 Adduct hardener and 34 parts by weight of benzyl alcohol mixed. The solvent-free varnish obtained results after curing tack-free and defect-free film surfaces.

100 parts by weight of the liquid epoxy resin mentioned in Example 10 based on bisphenol A (epoxy equivalent: 190) with 56 parts by weight of the adduct hardener described in Example 10 and 100 "lightweight tar (Pitch No. 4 of Union Carbide Corp. USA, viscosity at 15.5 ° C: 270 P) mixed. The resulting, solvent-free epoxy tar paint results after curing tack-free, glossy and defect-free film surfaces.

100 parts by weight of the liquid epoxy resin mentioned in Example 10 Based on bisphenol A (epoxy equivalent: 190), 56 parts by weight of that described in Example 10 are used Adduct hardener, 29 parts by weight of benzyl alcohol and 100 parts by weight of tar (Pitch No. 4 from Union Carbide Corp. USA, viscosity at 15.5 ° C: 270 P) mixed. The resulting solvent-free epoxy tar paint gives tack-free, glossy finish after curing and flawless film surfaces.

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Properties of the films obtained

The properties of the films obtained after a curing time of 21 days are listed in the following table:

Properties or
Test methods Epoxy resin hardener adduct system 10 B 10 C 10 D 10 E. 10 A 23 45 65 40 1. Surface hardness according to DIN
53157; "König pendulum hardness
at 20 ° C, test specimens are be
layered glass plates »Trok-
kenf film thickness 300 - 500 ^ um 110 > 10 10 > 10 > 10 2. Erichsen recess (DIN 53156)
Test specimens are coated
Iron sheets 110x70x1 mm, dry
ken film thickness 300-500 μm 7.7 1 1 1 1 3. Cross cut (DIN 53151)
Cutting distance 1 mm I.

Example 11

To 100 parts by weight of the hardener prepared according to Example 9, 56.5 parts by weight of cresyl glycidyl ethers are added with stirring (Epoxy equivalent 174-185) given slowly. The reaction mixture is then stirred at 100 ° C. for 1 hour. The so The viscous adduct hardener obtained is light yellow. Its H equivalent is 145.

Use of this adduct hardener for solvent-free 2-component epoxy resin paints

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100 parts by weight of a liquid epoxy resin based on bisphenol A (GRILONIT G 3, Emser-Werke AG, Switzerland) (epoxy equivalent: 190) are mixed with 76.5 parts by weight of the adduct hardener described in Example 11. The received After curing, solvent-free varnish results in tack-free, clear and fault-free film surfaces.

100 parts by weight of the liquid epoxy resin mentioned in Example 11A based on bisphenol A (epoxy equivalent: 190) with 76.5 parts by weight of the adduct hardener described in Example 11 and 30 parts by weight of benzyl alcohol mixed. The solvent-free varnish obtained results after curing tack-free, clear and flawless film surfaces.

Properties of the films obtained

The properties of the films obtained after a curing time of 21 days are listed in the following table:

Properties or
Test methods Epoxy resin hardener adduct
system 11 B 11 A 180
6.5
1 1. Surface hardness according to DIN
53157; Pendulum hardness according to König
at 20 ° C; Test bodies are be
laminated glass plates, dry
ken film thickness 300-500 ^ m
2. Erichsen recess (DIN 53156)
Test specimens are coated
Iron sheets 110x70x1 mm, dry
ken film thickness 300 - 500 μτα
3. Cross cut (DIN 53151)
Cutting distance 1 mm 195
6.0
1

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Claims (10)

Claims Condensation products suitable as hardeners for epoxy resins, characterized in that they are in the Ways to prepare that resulting from the oxidation of cycloalkanes, with primary and secondary Amines reactable by-products condensed with polyvalent aliphatic amines. 2. Hardener according to claim 1, characterized in that one obtained from the oxidation of cycloalkanes, By-products reactable with amines used those which form soluble salts with alkali metals (i.e. that contain acidic groups, especially COOH groups). 3. Hardener according to claims 1 to 2, characterized in that one for their production is used in the oxidation by-products of cyclohexane and methylcyclohexane which can be reacted with primary and secondary amines used. 4. Hardener according to claims 1 to 2, characterized in that one for their production in the oxidation of Cyclododecane accruing, with primary and secondary amines reactable by-products are used. 5. Hardener according to claims 1 to 4, characterized in that one for their production in the oxidation of Cycloalkanes with oxygen or containing oxygen By-products that occur in gases and react with primary and secondary amines are used. -30- 209849/1176 6. Hardener according to Claims 1 to 5, characterized in that the primary and secondary amines used for their preparation polyvalent aliphatic polyalkylenepolyamines of the formula I are used, H MIN A- ^ NH ₂ (I) in the A is a lower alkylene radical containing at least 2 carbon atoms, which is attached to the neighboring members with two different carbon atoms is bound, and η 2 to 6, in particular 2-4, and A occurring η times can be the same or different. 7. Hardener according to claims 1 to 6, characterized in that one acidic group of the resulting one for their production By-products can react with at least two primary and / or secondary amino groups. 8. Hardener according to claims 1 to 7, characterized in that the condensation is used for their preparation at a Temperature of 150-3OO ° C carries out. 9. Use of the hardener according to claims 1 to 8 for hardening compounds containing more than 1 epoxy group per molecule. 10. Embodiment according to claim 9, characterized in that that the compound containing more than one epoxy group per molecule is an epoxy resin based on 2,2-bis (hydroxyphenyl) propane and epichlorohydrin are used. 209849/1176